Wetting agent for alkaline mercerizing solutions



Patented Apr. 9, 1949 STAT S WETTING AGENT FOR *1 MERCERIZING SOLUTIONS Heinrich Lier, Basel, Switzerland, assignor to the firm Chemical Works formerly Sandoz, Basel,

Switzerland No Drawing. Application July 26, 1937, Serial 10 Claims.

It has been found that the wetting and penetrating action of alkaline lyes of at least 15 B., for example mercerizing lyes, is considerably improved if amides of naphthenic acids or naphthenic acid fractions or of ramified aliphatic carboxylic acids having at least 5 C atoms, which apart from those combined with the acid radical contain no further amino groups, are added thereto together with such alkali-soluble and alkali-stable substances as act as dispersing agents in concentrated lyes. Under the expression ramified aliphatic acids such aliphatic acids are meant the carbon chain of which is ramified or branched.

The use of mono-acylated ethylene-diamines which contain the radical of the naphthenic acid, in combination with phenols, is described in the German Patent No. 614,913. But owing to the non-acylated aliphatic bound amino group contained in these substances they are strong bases which form stable salts with acids, whereas according to the invention carboxylic acid amides without basic group, which do not form definable salts with either acids or alkalies, are used.

25 As the examples show, the effect obtained with the carboxylic acid amides is surprising and in view of their neutral character was not to be expected, as the effect of similar substances hitherto used for the same purpose, such as for example the free carboxylic acids themselves, is far surpassed by that of their amides.

The amides coming into question are those made from naphthenic acids or any naphthenic acid fractions or from the ramified aliphatic carboxylic acids, in any known manner by means -of ammonia or monoor polyvalent aliphatic or cycloaliphatic amines which may eventually still contain one or more hydroxyl groups.

The following are suitable as auxiliary, alkalistable, dispersing agents: alkali-stable, highly sulphonated oils, for example highly sulphonated castor oil; phenols as for example the cresols, especially metaand para-cresol, cresol mixtures, xylenols, xylenol mixtures, cresol-xylenol mix- 4 tures, ethyl phenols, propyl phenols, methylethyl phenols, methyl-propyl phenols as for example Carvacrol, phenols from wood-tar, tar phenols as mentioned in the British Patent No.

390,824 for example, synthetic phenol deriva- 50 tives as for example synthetically obtainable monoand polyalkyl phenols or sulfuretted phenols; the halogen substitution products of phenols as for example technical mixtures of monochlorinated cresols, o-chloro-m-cresol, o-chloro- 55 p-cresol, p-chloro-m-cresol, technical mono- In Switzerland August 3, 1936 chloro-xylenol mixtures, 2:4-dimethyl-6-chlorophenol and so forth, bromo-cresols, also C-alkoxy-derivatives of phenols as for example guaiacol and so forth, the naphthols, and any desired mixtures of all these phenols.

The following are suitable as auxiliary emulsifiers; the initial members of the homologous series of the aliphatic and the aromatic benzeneand phenolsulphonic acids, for example butane-, pentane-, isopentane-sulphonic acids, xylol-, cymenesulphonic acids, butyl-phenolsulphonic acids, the acid sulphuric acid esters of straight-chained or ramified alcohols with 4 to 10 C atoms, the acid sulphuric acid esters of etheralcohols with one or more etheric oxygen bridges as well as the true ether-sulphonic acids obtainable from these esters by reaction with sodium sulphite, further the glucoside-like derivatives from sugars and normal ramified aliphatic alcohols or ether-alcohols.

Ready prepared mixtures of the acid amides with the dispersing auxiliary substances, whose ratio of mixture can be varied within wide limits according to the purpose in view, are best adapted for carrying out the process. By choice of the ingredients and proportion of the mixture, it is possible to adapt the mixture to given conditions as regards lye concentration, lye temperature and resistance to wetting of the material to be treated, in such a way that clear, highly active lyes are obtained, which changes not at all or hardly at all in action, which are outstandingly adapted for carrying out alkalizations of all kinds, for examplev raw mercerization.

Generally, the presentinvention comprises a process for increasing the wetting-out power of alkaline lyes of more than 15 31%., consisting in adding to said lyes at least one amide of an aliphatic carboxylic acid selected from the class consisting of naphthenic and ramified aliphatic acids and at least one dispersing agent which is soluble and stable in alkaline solutions.

Another object of the invention consists in improved alkaline lyes of more than 15 B., containing at least one amide of an aliphatic carboxylic acid selected from the class consisting of naphthenic and ramified aliphatic acids and at least one dispersing agent which is soluble andstable in alkaline solutions.

Further the present invention comprises mixtures consisting of 40-1 per cent of at least one amide of an aliphatic carboxylic acid selected from the class consisting of naphthenic and ramified aliphatic acids and of 60-99 per cent of at least one dispersing agent which is soluble and limited to the details of the following examples.

EXAMPLE 1 If for the sake of comparison 1.2% by weight of each of the following mixtures are added to mercerizing lyes of 30 1%. at 15 C., a great superiority will be observed of the action of the amide over that of the carboxylic acid, both in its wetting and shrinking powers on raw, dry cotton. 4

- Mixture of Mixture of 88% by weight of technical cre- 88% by we1ght of techmcal cresol mixture sol mixture +12% by weight of technical +1 6 by weight of naphthenic ac d amide prepared from the naphthenic acid.

chloride of technical naphthenic acid and ammonia.

Dry raw fabrics are slowly and unevenly wetted through by the naphthenic acid containing lye, but are immediately and quite uniformly Wetted through by the naphtheic acid amide containing lye, so that they rapidly sink down and strongly shrink.

Shrinking diagrams (see Mcllzands Textz'lberichte vol. XII, Janf1931, pages -41) The shrinking tests were carried out with dry raw pearl yarn 3/2 using a weight of about 11 gms.; the percentages given below indicate the shrinkage achieved in the times indicated, as a percentage of the original length, and with the aforesaid mixtures, respectively:

Percent Percent After 15 sec 4.8 16. 4 After 30 sec. 12. 6 23. 9 After sec 16. 7 25. 8 After sec. 19. 0 26. 6 After 90 sec 21. 8 27. 6

EXAMPLE 2 Q 1.17% by weight of each of the following mix tures was added to a mercerizing lye of 32 B. and-the shrinking determined at 15 C. as in Example 1.

Mixture of by weight, of technical xylenol mixture +20% by weight of naphthcnio Mixture of- 90% by weight of technica xylenol mixture +10 0 by weight of naphthenic ac amide from technical naphthenic acid Shrinking diagrams (see Example 1) Percent Percent 6. 2 l5. 0 15. 6 24. 8 20. 2 27. 2 22. 6 28. 0 25. 2 as. 4 Lye clear Lye clear From the comparative tests it appears that the mixture containing only 10% of naphthenic acid amide acts better than that containing 20% of naphthenic acid.

EXAMPLE? If 1.3% by weight of a mixture of 90% by weight of a technical mixture of monochloro- I cresols and 10% by weight of naphthenic acid amide from technical naphthenic acid (as in Examples 1 and 2) is added to a lye of 30 B., a clear liquid is obtained of outstanding wetting and shrinking action. If the lye is diluted with of its volume of water and then evaporated in an open pan to its original concentration, its good action is hardly reduced at all.

Shrinking diagrams Freshly Diluted and prepared reevaporatcd Wetting tests with dry raw fabric Raw fabrics become wetted Raw fabrics become wetted through uniformly the mothrough uniformly the moment they are laid on the lye ment they are laid on the lye and sink down within 8-17 and sink down with 12-24 seconds. seconds.

EXAMPLE 4 If 0.8% by weight of a mixture consisting of 90% by weight of 3-bromo-4-oxy-l-methylbenzene (monobromo-p-cresol) and 10% by weight of naphthenic acid amide from technical naphthenic acid (as in Examples 1, 2 and 3) is added to a mercerizing lye of 30 B., the same acquires an excellent wetting and shrinking action on dry raw fabrics and yarns. This action is particularly surprising because monobromo-p-cresol, although preponderating in the mixture, by itself only brings about a very limited effect, so that the effect must be due to the very small content of naphthenic acid amide of only 0.8 part by weight per thousand.

Shrinking diagrams (raw pearl yam 3/2) 1% monobirloJmot; p-creso w on 1% mixture na hthenic ac d amide Percent Percent After 15sec 19.0 1. 4 After 30 sec- 25. 7 4. 4 After 45 sec- 27. 2 7. 6 After 60 sec- 27. 9 l0. 0 Altai-90sec.-- 28.4 15.0 Lye clear Lye clear Wetting tests with dry raw fabrics The raw fabrics remain floating on the lye after 8 minutes and are still partly dry.

The raw fabrics become wetted through uniformly in a moment and sink down in the lye within 10-30 seconds.

EXAMPLE 5 A mercerizing lye of 35 B. which contains 1.14% by weight of a mixture of by weight of technical cresol-xylenol mixture and of 15% by weight of naphthenic acid-di-n-propylamide (prepared from naphthenic acid chloride and difraction boiling between about 120-160" C. at a pressure of 8 mm. of mercury, by means of phosphorus trichloride) and contains 6.65% of nitrogen, is added to a mercerizing lye of 35 B. A clear liquid is obtained which after 24 hours open storage does not change either in it's character or its good action.

Wetting tests with dry raw cotton fabrics Freshly prepared lye lye open-stored for 24 hours The fabrics become wetted The fabrics become wetted through uniformly immedithrough uniformly immediately they are 1816. on the lye ately they are laid on the lye and sink down within 15-20 and sink down within 16-20 seconds. seconds.

Shrinking tests with dry raw pearl yarn 3 /2 15 cc. of a mixture of 95% by weight of technical xylenol mixture and 5% by weight of methylisobutylacetic acid acide are added per litre to a caustic soda lye of 30 B. A clear liquid is obtained of very high wetting and shrinking action on raw cotton yarns and fabrics.

Shrinking diagrams Per cent After 15 seconds 20.5 After 30 seconds 24.5 After 45 seconds 25.6 Lye clear After 60 seconds 26.1

Raw fabrics become wetted through uniformly the moment they are laid on the lye and sink down within 8-9 seconds.

EXAMPLE 8 A mixture of 90 parts by weight of an approximately 65% aqueous solution of the sodium salt of the acid sulphuric acid ester of ethyleneglycol-monobutyl-ether and parts by weight of a mixture of naphthenic acid amides prepared by reaction, with ammonia, of the naphthenic acid chloride mixture from a technical naphthenic acid fraction of the acid number of about 280, is added in a proportion of 1.5% by volume to a caustic soda lye of 28 B. A clear liquid is obtained, the extraordinarily effective action of which is by far not reached by similar use alone of the acid sulphuric acid ester. The shrinking of a dry Mako raw pearl yarn amounts after but seconds action to 21.8% of the original length, while in a comparative lye to which only 1.5% by volume of the sulphuric acid ester solution has been added, it only amounts to 15.0%.

EXAMPLE 9 A mixture of 95% by weight of technical high boiling xylenol mixture and 5% by weight of the reaction product of one molecule of ethyleneoxide and one equivalent part of the naphthenic acid amide mixture named in Example 8, when added in the proportion of 1.5% by volumeto a caustic soda lye of 30 B., yields a clear solution which immediately uniformly wets through raw twist fabrics and raw, undesized poplin, so that the fabrics sink down within about 8-11 seconds.

EXAMPLE 10 parts of the part remaining liquid of the amides obtained from a naphthenic acid mixture of the acid number 356, mixed with 80 parts of the concentrated aqueous solution of the sodium salt of a highly sulphonated castor oil, yield a product of high wetting power in a caustic soda lye of 30 B. A still higher effect is obtained with a mixture of 10 parts of the liquid or solid part of the above named naphthenic acid amide with 90 parts of a technical xylenol' mixture.

' EXAMPLE 11 A mixture of 88% by weight of a raw, technical naphthenic acid of the acid number 304, which contains about 10-15% of phenol-like impurities, and of 12% by weight of the naphthenic acid amide mixture named in Example 8, when added in the proportion of 15 cc. per litre to caustic soda lye of 20 B., yields a considerably greater efiicacity than when 15 cc. per litre of the raw technical naphthenic acid alone are added. Raw, undesized pieces of poplin are immediately uniformly wetted through in the first lye, so that they sink downwithin 17-24 seconds, while in a similar lye free from naphthenic acid amide they are only wetted non-uniformly and sink down only after about 1% minutes.

EXAMPLE 12 18 grams of a mixture of 90% by weight of N-di-(cr' -dioxypropyl) aniline (prepared from 1 molecule of aniline and 2 molecules of glycide) and of 10% by weight of the mixture of amides prepared from a high-boiling technical naphthenic acid fraction of the acid number 259, are added per litre to a caustic soda lye of 25 B. After short stirring a clear liquid is obtained in which a raw Mako pearl yarn 3/2 shrinks for 18% after 15 seconds and for 20.8% after seconds, in respect of its original length. In a comparative lye in which 18 grams per litre of the N-di-(fiz' -dioxypropyl) aniline alone have been dissolved, the shrinkings amount to only 1.4% and 3.4% of the original length after periods of action of 15 and 30 seconds respectively.

EXAMPLE 13 93% by weight of isoamylglucoside and 7% by weight of the naphthenic acid amide named in Example 12 are mixed together and 18 grams thereof are added per litre to a caustic soda lye of 28 B. or 18 grams thereof per litre to a caustic potash lye of 32 B.; clear liquids of good wetting and penetrating powers on raw yarns and fabrics are thereby obtained.

EXAMPLE 14 1.5% by volume of a mixture of 96% by weight of the 40% aqueous solution of technical sodium cymene sulphonate and of 4% by weight of the naphthenic acid amide mixture named in Example 12, is added to a caustic soda lye of 25 B. at 30 C. The clear lye has a high wetting and penetrating power on raw fab ics and yarns. A Mako raw pearl yarn 3/2 undergoes a shrinkage of 15.6% of the original length after but 15 seconds action as compared with that of only 11.3% in a lye to which 1.5% by volume of the plain solution of the sodium cymene sulphonate has been added.

awacea mmrm 15 A mixture of 90 parts by weight of N-difiv -dloxypropyl) isoamylamine (prepared from molecule of isoamylamine and 2 molecules of :lycide) and parts by weight of the amide nixture prepared from technical naphthenic acid mixture of the acid number 273 is added in he proportion of grams per litre to a caustic oda lye of B. A clear lye is obtained in vhich a Make raw pearl yarn 3/2 shrinks for 22.8% of its original length after but 15 secnds treatment. In a similar lye to which 15 :rams per litre of the oxyamine alone have been ldded the shrinkage after the same period mounts to but 14.8% of the original length.

What I claim is:

1. Mercerizing lyes of more than 15 B., conaining at least one amide, free from basic :roups and sulphonic acid groups of an aliphatic :arboxylic acid selected from the class consistng of naphthenic and branched-chain aliphatic :arboxylic acids having at least 5 carbon atoms Lnd at least one dispersing agent which is solu- )le and stable in alkaline solutions.

2. Mercerizing lyes of more than 15 B., conaining at least one amide, free from basic :roups and sulphonic acid groups of a naphthenic LCid and at least one dispersing agent which is oluble and stable in alkaline solutions.

3. Mercerizing lyes of more than 15 B., conaining 0.5 to 2 per cent of a mixture consistng of -1 per cent of the mixture of amides ree from basic groups and sulfonic acid groups, u'epared from naphthenic acids of the acid num- )81 of 230-280 and of -99 per cent of a techlical xylenol mixture. 1 4. Mercerizing lyes of more than 15 B., conaining 0.5 to 2 per cent of a mixture consistng of 40-1 per cent of the mixture of amidem ree from basic groups and sulfonic acid groups, repared from naphthenic acids of theacid numier of 230-280 and of 60-99 per cent of a techiical monochlorocresol mixture.

5. Mercerizing lyes of more than 15 B., con- ,aining 0.5 to 2 per cent of a mixture consistng of 40-1 per cent of the mixture of amides free from basic groups and sulfonic acid groups, prepared from naphthenic acids of the acid number of 230-280 and of 60-99 per cent of the sulphuric acid ester of ethyleneglycolmonobutylether.

6. As new compositions of matter the mixtures consisting of 40-1 per cent of at least one amide, free from basic groups and sulfonic acid groups of an aliphatic carboxylic acid selected from the class consisting of naphthenic and branched-chain aliphatic carboxylic acids having at least 5 carbon atoms and of 60-99 per cent of at least one dispersing agent which is soluble and stable in alkaline solutions, said mixtures being valuable products for increasing the Wetting-out power of mercerising lyes of more than 15 B.

7. As new compositions of matter the mixtures consisting of 40-1 per cent of at least one amide, free from basic groups and sulfonic acid groups of a naphthenic acid and of 60-99 per cent of at least one dispersing agent which is soluble and stable in alkaline solutions, said mixtures being valuable products for increasing the wetting-out power of mercerizing lyes of more than 15 B.

8. As new compositions of matter the mixtures consisting of 40-1 per cent of the mixture of amides, free from basic groups and sulfonic acid groups, prepared from naphthenic acids of the acid number of 230-280 and of 60-99 per cent of a technical xylenol mixture.

' 9. As new compositions of matter the mixtures consisting of 40-1 per cent of the mixture of amides, free from basic groups and sulfonic acid groups, prepared from naphthenic acids of the acid number 2130-280 and of 60-99 per cent of a technical monochlorocresol mixture.

10. As new compositions of matter the mixtures consisting of 40-1 per cent of the mixture of amldesyfree from basic groups and sulfonic acid groups, prepared from naphthenic acids of the'acid number of 230-280 and of 60-99 per cent of the sulphuric acid ester of ethylenegly-.

colmonobutylether.

HEINRICH LIER. 

